Synthesis, Structure and Reactivity of Homo- and Heterobimetallic Complexes of the General Formula [Cp*Ru(m-Cl)3ML] (LM = (arene)Ru, Cp*Rh, Cp*Ir)

The homo- and heterobimetallic complexes [CpRu(m-Cl)3-ML] [LM = (C6H6)Ru, (cymene)Ru, (1,3,5-C6H3iPr3)Ru, CpRh, CpIr] were prepd. by reaction of [CpRu(m-OMe)]2 with Me3SiCl and subsequent addn. of [LMCl2]2. The complexes [CpRu(m-Cl)3Ru(cymene)] and [CpRu(m-Cl)3-IrCp*] were characterized by single-crystal X-ray analyses. In crossover expts. with [CpRh(m-Cl)3RuCl(PPh3)2] and [CpRu(m-Cl)3Ru(1,3,5-C6H3iPr3)] in CD2Cl2, a dynamic equil. with the complexes [CpRh(m-Cl)3RuCp] and [(1,3,5-C6H3iPr3)Ru(m-Cl)3RuCl(PPh3) 2] was rapidly established, demonstrating the kinetic lability of the triple chloro bridge. Upon reaction of [CpRh(m-Cl)3RuCp] with benzene, the ionic complex [CpRu(C6H6)][CpRhCl3] was formed, which was characterized by X-ray crystallog.